CN102380340A - Desulfurizer and preparation method thereof - Google Patents
Desulfurizer and preparation method thereof Download PDFInfo
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- CN102380340A CN102380340A CN2010102740163A CN201010274016A CN102380340A CN 102380340 A CN102380340 A CN 102380340A CN 2010102740163 A CN2010102740163 A CN 2010102740163A CN 201010274016 A CN201010274016 A CN 201010274016A CN 102380340 A CN102380340 A CN 102380340A
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Abstract
The invention provides a desulfurizer, wherein the desulfurizer comprises zinc oxide, sodium carbonate and an adhesive. The invention also provides a preparation method of the desulfurizer; the method comprises forming and activation of a raw material mixture; and the raw material mixture comprises zinc oxide, sodium carbonate and an adhesive. During purification of a propylene crude product, sulfur-containing compounds can be fully removed by using the desulfurizer provided by the invention, and thus a high-purity propylene product with very low sulfur content can prepared.
Description
Technical field
The present invention relates to the preparation method of a kind of desulfurizing agent and this desulfurizing agent.
Background technology
Usually, the liquid hydrocarbon that produces in the oil-refining chemical industry (reduced pressure distillation process as usual, catalytic cracking process, heavy oil catalytic cracking process or delay coking process) contains mercaptan, cos (COS), H
2S and CS
2Deng sulfur-containing compound, these sulfur-containing compounds can mix in the organic compound products such as propylene, propane or ethane by this liquid hydrocarbon preparation, thereby have reduced the quality of the organic compound product of preparation.Therefore,, need remove, to improve the organic compound product gas purity of preparation to these sulfur-containing compounds adopting said liquid hydrocarbon to prepare in the process of organic compound product.Yet, in the actual production process, H
2Thereby S can generate the thioether that traditional organic desulfurizing agent is difficult to remove with olefine reaction, and COS and CS
2It itself also is the sulfur-containing compound that adopts traditional organic desulfurizing agent to be difficult to remove.
For this reason; CN 101319149A discloses and a kind of liquid hydrocarbon that delayed coking unit produces has been carried out preliminary treatment earlier, then remakes the raw material into gas fractionation unit, processes the method for producing propylene, propane, C-4-fraction; Wherein, Utilize coking liquid hydrocarbon that amine liquid removes hydrogen sulfide before carrying out gas fractionation unit, carry out the alkali cleaning water elution earlier and remove mercaptan and remove low amounts of water, advance the COS hydrolytic decomposition pot again and carry out desulfurization; Then remove the hydrogen sulfide that hydrolysis produces again, air inlet body fractionating device is processed as raw material again.
In above-mentioned patent application, the hydrogen sulfide that produces after the desulfurization of liquid hydrocarbon process COS hydrolytic decomposition pot is to adopt traditional hydrogen sulfide desulphurization agent to remove.Yet these traditional hydrogen sulfide desulphurization agents are difficult to fully remove the hydrogen sulfide in the said liquid hydrocarbon, make that the sulfur content in the final organic compound product for preparing is still higher.
CN 1120970A discloses a kind of novel normal low-temp desulfurization agent, and it comprises three kinds of following oxide weights compositions: ZnO 85-95%, Na
2O 0.1-10%, Al
2O
30.1-10%.Though the desulfurizing agent in this patent application has the ability that removes hydrogen sulfide of obvious raising with respect to amine liquid; Yet; The Sulfur capacity of this desulfurizing agent is still not high; Thereby, this desulfurizing agent is used for the process that liquid hydrocarbon prepares organic compound products such as propylene still is difficult to prepare organic compound products such as highly purified propylene.
Summary of the invention
The present invention adopts existing desulfurizing agent the thick product of propylene to be carried out be difficult to fully remove in the process of purifying the defective of sulfur-containing compound wherein in order to overcome; A kind of new desulfurizing agent and the preparation method of this desulfurizing agent are provided; In that thick product carries out in the process of purifying adopting this desulfurizing agent can fully remove sulfur-containing compound wherein to propylene, thereby can obtain the very low highly purified propylene product of sulfur content.
The invention provides a kind of desulfurizing agent, wherein, this desulfurizing agent contains zinc oxide, sodium carbonate and adhesive.
The present invention also provides a kind of preparation method of desulfurizing agent, and this method comprises carries out moulding and activation with a kind of raw mix, and said raw mix contains zinc oxide, sodium carbonate and adhesive.
In said desulfurizing agent provided by the invention, owing to contain zinc oxide and sodium carbonate, thus have very high Sulfur capacity, and then to H
2S and CS
2Has the very strong ability that removes.Therefore, in that thick product carries out in the process of purifying adopting said desulfurizing agent provided by the invention can fully remove sulfur-containing compound wherein to propylene, thereby can prepare the very low highly purified propylene product of sulfur content.In the present invention, said Sulfur capacity is meant the total amount of the sulphur of Unit Weight desulfurizing agent ability effective elimination.
The specific embodiment
Desulfurizing agent according to the present invention contains zinc oxide, sodium carbonate and adhesive.In said desulfurizing agent; The content of said zinc oxide, sodium carbonate and adhesive does not have special qualification, yet, have higher Sulfur capacity for making said desulfurizing agent; Thereby has the stronger ability that removes sulfur-containing compound; Gross weight with said desulfurizing agent is a benchmark, and the content of said zinc oxide is preferably 65-90 weight %, further is preferably 70-80 weight %; The content of said sodium carbonate is preferably 5-20 weight %, further is preferably 10-15 weight %; The content of said adhesive is preferably 3-20 weight %, further is preferably 5-15 weight %.
In said desulfurizing agent, the adhesive in the said desulfurizing agent can be the various adhesives that routine is used, for example can be in kaolin, sodium metaaluminate, the sweet soil of sheep and the diatomite at least a.Under preferable case, said adhesive is a sodium metaaluminate, thereby makes said desulfurizing agent have higher Sulfur capacity.
The present invention also provides a kind of preparation method of desulfurizing agent, and this method comprises carries out moulding and activation with a kind of raw mix, and said raw mix contains zinc oxide, sodium carbonate and adhesive.
In a kind of preferred implementation,, in said raw mix, add zinc carbonate in order further to improve the Sulfur capacity of prepared desulfurizing agent.Said zinc carbonate can play the reaming effect, thereby makes the desulfurizing agent of final preparation have the pore volume and the bore dia of increase, and then improves the Sulfur capacity of said desulfurizing agent.
In the process of the said desulfurizing agent of preparation; The addition of said zinc carbonate does not have special qualification; Yet, for the Sulfur capacity of the desulfurizing agent that significantly improves final preparation, with respect to the said raw mix of 100 weight portions; The addition of said zinc carbonate is preferably the 1-15 weight portion, more preferably the 3-12 weight portion.
In the process of the said desulfurizing agent of preparation, the method for said moulding does not have special qualification in the present invention, can adopt conventional forming method to implement, and the method for said moulding for example can be extrusion molding.
In the process of the said desulfurizing agent of preparation, the method for said activation can be included under the inert gas atmosphere at 120-500 ℃ of following heat treatment 1-5 hour; In a kind of preferred implementation, in the mixture of said zinc oxide, sodium carbonate and adhesive, added under the situation of zinc carbonate, the method for said activation was included under the inert gas atmosphere at 350-450 ℃ of following heat treatment 1-5 hour.Said heat treatment is through implementing in the environment that the article shaped that obtains after the said moulding is positioned over said temperature scope (be 120-500 ℃, be preferably 350-450 ℃).Under above-mentioned activation condition, zinc carbonate decomposes, and generates carbon dioxide and zinc oxide, and said zinc oxide is used for the active component of the said desulfurizing agent of supply.The gas of said inert gas under 120-500 ℃, not reacting with said zinc oxide, sodium carbonate and adhesive.Said inert gas can be in nitrogen, argon gas, helium and the neon at least a.
Below through embodiment invention is described further, but the present invention is not limited only to this.
Embodiment 1
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Zinc oxide, 11 weight parts of sodium carbonate, the zinc carbonate of 11 weight portions, the sodium metaaluminate of 11 weight portions and an amount of water of 67 weight portions are mixed; Process mixed slurry; Use the double screw extruder extrusion molding then, and 120 ℃ down dry, afterwards in activation 2 hours under nitrogen protection under 380 ℃; Be cooled to room temperature afterwards, thereby obtain desulfurizing agent A1.
Embodiment 2
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Zinc oxide, 14 weight parts of sodium carbonate, the zinc carbonate of 7 weight portions, the kaolin of 14 weight portions and an amount of water of 65 weight portions are mixed; Process mixed slurry; Use the double screw extruder extrusion molding then, and 120 ℃ down dry, afterwards in activation 1.5 hours under nitrogen protection under 450 ℃; Be cooled to room temperature afterwards, thereby obtain desulfurizing agent A2.
Embodiment 3
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Zinc oxide, 10 weight parts of sodium carbonate, the zinc carbonate of 3 weight portions, the sweet soil of sheep of 10 weight portions and an amount of water of 77 weight portions are mixed; Process mixed slurry; Use the double screw extruder extrusion molding then, and 120 ℃ down dry, afterwards in activation 2.5 hours under argon shield under 400 ℃; Be cooled to room temperature afterwards, thereby obtain desulfurizing agent A3.
Embodiment 4
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares desulfurizing agent, and different is in the process of preparation desulfurizing agent, not use zinc carbonate, thereby obtain desulfurizing agent A4.
Embodiment 5
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares desulfurizing agent, and different is, the consumption of sodium carbonate is 2 weight portions in the process of preparation desulfurizing agent, and the consumption of zinc oxide is 76 weight portions, thereby obtains desulfurizing agent A5.
Embodiment 6
Present embodiment is used to explain said desulfurizing agent provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares desulfurizing agent, and different is, the consumption of sodium carbonate is 25 weight portions in the process of preparation desulfurizing agent, and the consumption of zinc oxide is 53 weight portions, thereby obtains desulfurizing agent A6.
Comparative Examples 1
Method according to embodiment 1 prepares desulfurizing agent, and different is in the process of preparation desulfurizing agent, not use sodium carbonate, and replace said sodium carbonate with the zinc oxide of identical weight, thereby obtain desulfurizing agent D1.
Comparative Examples 2
With the basic zinc carbonate of 160 weight portions 400 ℃ of following roastings 3 hours; To the water of the sodium metaaluminate of the sodium carboxymethylcellulose pyce of the basic zinc carbonate that wherein adds 13 weight portions, 1 weight portion, 9 weight portions and 36 weight portions and mix; Then the mixture that obtains is used the double screw extruder extrusion molding; Dry down at 100 ℃; Then 400 ℃ of following roastings 3 hours, thereby obtain containing the desulfurizing agent D2 of aluminium oxide of sodium oxide molybdena and 4.62 weight % of zinc oxide, the 2.81 weight % of 92.57 weight %.
Test case
(1) preparation crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 23 weight % gets in the absorption tower; The inlet amount of said liquid hydrocarbon is 32 tons/hour; The inlet amount of the aqueous solution of said N methyldiethanol amine is 10 tons/hour; Temperature in the said absorption tower is 30 ℃, and pressure is 1.2MPa.Then; The NaOH aqueous solution of isolating liquid hydrocarbon and concentration from the bottom on said absorption tower and be 20 weight % gets into the extraction tower with cat head at the bottom of tower respectively; The inlet amount of said liquid hydrocarbon is 35 tons/hour; The inlet amount of the said NaOH aqueous solution is 8 tons/hour, and the temperature in the said extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon that obtains after the washing is got in the gas fractionator carry out fractionation, obtaining the thick product of propylene, record the sulfur-containing compound that contains 28ppm in the thick product of said propylene according to the method for GB3392-82.In the present invention, ppm is meant percentage by weight.
Table 1
(2) preparation hydrolytic reagent
With the alumina support of 100 weight portions (available from Wuhan Hezhong Bio-chemical Manufature Co., Ltd.; Average pore diameter is 15 nanometers) thorough impregnation is in unsaturated carbonate potassium solution 2 hours; Make the alumina support that is adsorbed with solution of potassium carbonate dry under 100 ℃ then, with potash at said alumina support load 15 weight portions.Then, make alumina support that load has potash in activation 3 hours under protection of nitrogen gas under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent.
(3) purifying of propylene
Making the thick product of propylene that obtains in above-mentioned (1) is 1.0h with the weight space velocity
-1Get into successively the desulfurizing agent A1 be filled with 6 tons fixed bed reactors a (ratio of height to diameter is 4.5), be filled with 8 tons of aluminium oxide fixed bed reactors b (ratio of height to diameter is 4.5), be filled with the fixed bed reactors c (ratio of height to diameter is 4.5) of the hydrolytic reagent that obtains in 10 tons above-mentioned (2) and be filled with the fixed bed reactors d (ratio of height to diameter is 4.5) of the desulfurizing agent A1 of 10 tons of grams; Temperature in the said fixed bed reactors a is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed bed reactors b is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed bed reactors c is 5 ℃, and pressure is 1.2MPa; Temperature in the said fixed bed reactors d is 5 ℃, and pressure is 1.2MPa; Collect through the product after the said fixed bed reactors d processing as propylene product P1.
Adopt the desulfurizing agent D1-D2 of the desulfurizing agent A2-A6 for preparing among the embodiment 2-6 and Comparative Examples 1-2 preparation to replace the desulfurizing agent A1 of preparation among the embodiment 1 to carry out the propylene purifying respectively, thereby obtain propylene product P2, P3, P4, P5, P6, PD1 and PD2 respectively.
(4) sulfide content in the detection propylene product
Detect the content of the sulfur-containing compound among propylene product P1-P6 and the PD1-PD2 respectively according to the method for GB3392-82, its testing result is as shown in table 2 below.
Table 2
| The desulfurizing agent that adopts in the purge process | A1 | A2 | A3 | A4 | A5 | A6 | D1 | D2 |
| Propylene product | P1 | P2 | P3 | P4 | P5 | P6 | PD1 | PD2 |
| The content of the sulfur-containing compound in the propylene product (ppm) | 1.0 | 1.5 | 1.6 | 2.3 | 1.8 | 2.1 | 4.8 | 3.9 |
Data by table 2 can find out, in the purge process of propylene, adopt said desulfurizing agent provided by the invention to carry out desulfurization and in the propylene product that obtains the content of sulfur-containing compound very low, thereby can prepare highly purified propylene product.
Claims (10)
1. a desulfurizing agent is characterized in that, this desulfurizing agent contains zinc oxide, sodium carbonate and adhesive.
2. desulfurizing agent according to claim 1 wherein, is a benchmark with the gross weight of said desulfurizing agent, and the content of said zinc oxide is 65-90 weight %, and the content of said sodium carbonate is 5-20 weight %, and the content of said adhesive is 3-20 weight %.
3. desulfurizing agent according to claim 2 wherein, is a benchmark with the gross weight of said desulfurizing agent, and the content of said zinc oxide is 70-80 weight %, and the content of said sodium carbonate is 10-15 weight %, and the content of said adhesive is 5-15 weight %.
4. according to any described desulfurizing agent among the claim 1-3, wherein, said adhesive is at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and the diatomite.
5. the preparation method of any described desulfurizing agent among the claim 1-4 is characterized in that, this method comprises carries out moulding and activation with a kind of raw mix, and said raw mix contains zinc oxide, sodium carbonate and adhesive.
6. method according to claim 5 wherein, also contains zinc carbonate in the said raw mix.
7. method according to claim 6, wherein, with respect to the said raw mix of 100 weight portions, the consumption of said zinc carbonate is the 1-15 weight portion.
8. method according to claim 7, wherein, with respect to the said raw mix of 100 weight portions, the consumption of said zinc carbonate is the 3-12 weight portion.
9. according to any described method among the claim 5-8, wherein, the method for said activation was included under the inert gas atmosphere at 120-500 ℃ of following heat treatment 1-5 hour.
10. method according to claim 9, wherein, the method for said activation was included under the inert gas atmosphere at 350-450 ℃ of following heat treatment 1-5 hour.
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|---|---|---|---|
| CN 201010274016 CN102380340B (en) | 2010-09-06 | 2010-09-06 | Desulfurizer and preparation method thereof |
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| CN102380340B CN102380340B (en) | 2013-06-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703134A (en) * | 2012-05-14 | 2012-10-03 | 太原理工大学 | Method for preparing medium-high temperature gas desulfurizing agent by microwave radiation |
| CN105813738A (en) * | 2013-12-17 | 2016-07-27 | 三井化学株式会社 | Molded body, method for producing same, catalyst for alpha-olefin dimerization, and method for producing alpha-olefin dimer |
| CN115634713A (en) * | 2022-10-26 | 2023-01-24 | 浙江誉衡环保科技有限公司 | Desulfurization synergist for flue gas desulfurization and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100015A (en) * | 1986-01-06 | 1987-07-15 | 中国石油化工总公司石油化工科学研究院 | Hydro carbons low temperature liquid phase sweetening agent |
| US5358921A (en) * | 1989-06-07 | 1994-10-25 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
-
2010
- 2010-09-06 CN CN 201010274016 patent/CN102380340B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100015A (en) * | 1986-01-06 | 1987-07-15 | 中国石油化工总公司石油化工科学研究院 | Hydro carbons low temperature liquid phase sweetening agent |
| US5358921A (en) * | 1989-06-07 | 1994-10-25 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703134A (en) * | 2012-05-14 | 2012-10-03 | 太原理工大学 | Method for preparing medium-high temperature gas desulfurizing agent by microwave radiation |
| CN102703134B (en) * | 2012-05-14 | 2013-12-11 | 太原理工大学 | Method for preparing medium-high temperature gas desulfurizing agent by microwave radiation |
| CN105813738A (en) * | 2013-12-17 | 2016-07-27 | 三井化学株式会社 | Molded body, method for producing same, catalyst for alpha-olefin dimerization, and method for producing alpha-olefin dimer |
| CN105813738B (en) * | 2013-12-17 | 2018-08-28 | 三井化学株式会社 | The manufacturing method of formed body and its manufacturing method, alpha-olefin dimerization catalyst and alpha-olefin dimer |
| CN115634713A (en) * | 2022-10-26 | 2023-01-24 | 浙江誉衡环保科技有限公司 | Desulfurization synergist for flue gas desulfurization and preparation method thereof |
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| CN102380340B (en) | 2013-06-19 |
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Application publication date: 20120321 Assignee: SINOPEC CATALYST CO., LTD. Assignor: Sinopec Corp. Contract record no.: 2014990000622 Denomination of invention: Desulfuration agent and preparation method and application thereof Granted publication date: 20130619 License type: Exclusive License Record date: 20140805 |
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